107-94-8Relevant articles and documents
Atom- and Mass-economical Continuous Flow Production of 3-Chloropropionyl Chloride and its Subsequent Amidation
Movsisyan, Marine,Heugebaert, Thomas S. A.,Roman, Bart I.,Dams, Rudolf,Van Campenhout, Rudy,Conradi, Matthias,Stevens, Christian V.
, p. 11779 - 11784 (2018)
3-Chloropropionyl chloride is a chemically versatile building block with applications in the field of adhesives, pharmaceuticals, herbicides and fungicides. Its current production entails problems concerning safety, prolonged reaction times and the use of excessive amounts of chlorinating reagents. We developed a continuous flow procedure for acid chloride formation from acrylic acid and a consecutive 1,4-addition of hydrogen chloride generating 3-chloropropionyl chloride, as presented in this paper. Up to 94 % conversion was reached in 25 minutes at mild temperatures and pressures. This continuous flow method offers a safer alternative and is highly efficient in terms of consumption of starting product and shorter residence time. Valorization of this building block is exemplified by the synthesis of beclamide, a compound with sedative and anticonvulsant properties. Over 80 % conversion towards this drug was achieved in 1 minute in a continuous flow setup. Further research is needed to telescope the synthesis of 3-chloropropionyl chloride and subsequent beclamide formation without intermediate purification.
Initiation of Cationic Polymerization of Cyclic Ethers by Redox Radical-Chain Reactions of Onium Salts
Kampmeier, J. A.,Nalli, Thomas W.
, p. 1381 - 1388 (1994)
Redox radical-chain reactions of diaryliodonium halides (Ar2I(+)X(-)) with tetrahydrofuran (THF) and 1,3-dioxolane to give arenes (ArH) and iodoarenes (ArI) are reported.When the reactions are initiated by irradiation at 313 nm, the quantum yield for the formation of iodoarene is substantially greater than 1 (Φ ca. 2-20).Nonphotochemical radical initiators give the same reaction, showing that the photochemical step is simply an initiation step.The key propagation step in these reactions is a single-electron reduction of the onium salts by ether-derived radicals.The photoinitiated reaction with THF follows zero-order kinetics, showing that termination does not compete with electron transfer.In addition, the same nonphotochemical conditions that give radical-chain reduction of the diaryliodonium halides give rapid cationic polymerization of the ethers when the iodonium hexafluorophosphates are used.These observations establish the connection between the redox chemistry of the iodonium salt and the cationic polymerization of the eters.The polymerization of THF by iodonium salt in the presence of free radicals is accelerated by the addition of trimethyl phosphite (TMP).Furthermore, triarylsulfonium salts will initiate polymerization of THF in the presence of TMP and radical sources.Therefore, redox-chain reduction of these onium salts by TMP can also initiate cationic polymerization of the cyclic ethers.
Effect of Structure and Substituents in the Aqueous Phase Oxidation of Alcohols and Polyols Over Au, Pd, and Au-Pd Catalysts
Rodriguez, Abraham A.,Williams, Christopher T.,Monnier, John R.
, p. 750 - 756 (2015)
Abstract Reactivity trends for oxidation of various alcohols and polyols have been examined for carbon-supported Au, Pd, and Au-Pd catalysts. A Hammett σρ approach was used to study substituent effects, with Hammett factors (ρ) of 1.27, 1.31, and 0.40 obtained for Pd, Au, and Au-Pd catalysts, suggesting the formation of a net negative charge at the transition state of the rate limiting step. The lower ρ for the Au-Pd catalyst versus Au and Pd monometallic catalysts indicates the ability of the Au-Pd catalyst to stabilize the negative charge at the transition state, explaining the improved performance of Au-Pd bimetallic catalysts for alcohol oxidation. Hammett-Taft factors were used to explain the low selectivity of terminal diols and polyols to diacids.
Gas-Phase Elimination Kinetics of Ethyl Esters of Chloroacetate, 3-Chloropropionate, and 4-Chlorobutyrate. The Electronic Effects of Substituents at the Acyl Carbon
Chuchani, Gabriel,Triana, Juana L.,Rotinov, Alexandra,Caraballo, Darlo F.
, p. 1243 - 1245 (1981)
Several ethyl chloroesters were pyrolyzed in a static reactor in the presence of a propene inhibitor at temperatures between 360 and 420 deg C and pressures between 49 and 209 torr.The reactions are homogeneous, unimolecular, and follow a first-order rate law.The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for ethyl chloroacetate, log k(s-1) = (12.70+/-0.50) - (197.0+/-6.1)kJ mol-1 (2.303RT)-1; for ethyl 3-chloropropionate, log k(s-1) = (12.54+/-0.22) - 196.8+/-2.7) kJ mol-1 (2.303RT)-1; and ethyl 4-chlorobutyrate, log k(s-1) = (12.67+/-0.31) - (198.7+/-3.8) kJ mol-1 (2.303RT)-1.The data from the rate coefficients give an approximate correlation only with ?* values (ρ*=0.357, r=0.903, and intercept =0.048 at 400 deg C).The present work together with those reported in the literature suggests, that electron-withdawing substituents at the acyl carbon of ethyl, isopropyl, and tert-butyl esters of substituted acetates enhance the rate of elimination, whereas electron-releasing substituents decrease it.
Preparation method of 3-chloropropionyl chloride
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Paragraph 0017-0019; 0021-0023; 0025-0027, (2021/05/08)
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 3-chloropropionyl chloride. The preparation method provided by the invention comprises the following steps: 1) introducing hydrogen chloride gas into acrylic acid to carry out addition reaction, and keeping the gas introduction pressure to be less than or equal to 0.15 MPa to obtain a reaction solution; and 2) pumping the reaction liquid in the step 1) into a reaction kettle in vacuum, heating to 30-80 DEG C, dropwise adding thionyl chloride, carrying out negative pressure distillation to 70 DEG C after dropwise adding is finished, and collecting a steamed product at 70-80 DEG C, namely the finished product 3-chloropropionyl chloride. According to the preparation method of the 3-chloropropionyl chloride, the process is simple, the preparation of the 3-chloropropionyl chloride can be realized by adopting extremely simple equipment, the cost is greatly reduced, the total yield (based on acrylic acid) is 90-92%, and the content is greater than or equal to 98.5%.
A production device for 5-chloro-indanone and a production method thereof
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Paragraph 0023, (2019/04/10)
The present invention relates to a production device for 5-chloro-indanone, including an acrylic acid storage tank, at least two gas liquid reactors connected in series, a thionyl chloride storage tank, at least two first flow reactors connected in series, a 3-chloropropionyl chloride storage tank, a chlorobenzene storage tank, at least two second flow reactors connected in series, and at least two third flow reactors connected in series. A gas outlet of each first flow reactor is connected to a gas inlet of the gas liquid reactor at the rearmost end through a pipeline provided with a condenser. A feeding port of the second flow reactor in the front end is provided with a first aluminium chloride feeding device. A feeding port of the third flow reactor in the front end is provided with a second aluminium chloride feeding device. The invention relates to a method for producing the 5-chloro-indanone by utilizing the production device. The production device and method can achieve continuous cyclic production and a high product yield.
3 - Chloropropionyl production device
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Paragraph 0016; 0020; 0021; 0022, (2019/06/24)
The utility model relates to a 3 - chloropropionyl production device, including acrylic acid storage tank, at least two serially connected gas-liquid reactor, thionyl chloride storage tank, at least two serially connected continuous reactor and 3 - chloropropionyl storage tank; acrylic acid storage tank with the discharge port of the foremost end of the pipeline located in the gas-liquid reactor is connected with feed opening; at the last end of the discharge port of the gas-liquid reactor through the pipeline with the locates at foremost a continuous reactor connected to the feed ports of the, the discharge port of the thionyl chloride storage tank through the pipeline with the locates at foremost a continuous reactor is connected with feed opening; at the last end of the discharge port of the continuous reactor through the pipeline with 3 - chloropropionyl connected to the feed ports of the storage tank; the air outlet of the continuous reactor is provided with a condenser through a pipeline with the last end of the gas-liquid located connected with the inlet of the reactor. The utility model of the 3 - chloropropionyl production equipment to achieve continuous circulation production, high product yield.
Catalytic Bromination of Alkyl sp3C-H Bonds with KBr/Air under Visible Light
Zhao, Mengdi,Lu, Wenjun
supporting information, p. 5264 - 5267 (2018/09/12)
Alkyl sp3C-H bonds of cycloalkanes and functional branch/linear alkanes have been successfully brominated with KBr using air or O2 as an oxidant at room temperature to 40 °C. The reactions are carried out in the presence of catalytic NaNO2 in 37% HCl (aq)/solvent under visible light, combining aerobic oxidations and photochemical radical processes. For various alkane substrates, CF3CH2OH, CHCl3, or CH2Cl2 is employed as an organic solvent, respectively, to enhance the efficiency of bromination.
Visible Light-Induced Oxidative Chlorination of Alkyl sp3 C-H Bonds with NaCl/Oxone at Room Temperature
Zhao, Mengdi,Lu, Wenjun
supporting information, p. 4560 - 4563 (2017/09/11)
A visible light-induced monochlorination of cyclohexane with sodium chloride (5:1) has been successfully accomplished to afford chlorocyclohexane in excellent yield by using Oxone as the oxidant in H2O/CF3CH2OH at room temperature. Other secondary and primary alkyl sp3 C-H bonds of cycloalkanes and functional branch/linear alkanes can also be chlorinated, respectively, under similar conditions. The selection of a suitable organic solvent is crucial in these efficient radical chlorinations of alkanes in two-phase solutions. It is studied further by the achievement of high chemoselectivity in the chlorination of the benzyl sp3 C-H bond or the aryl sp2 C-H bond of toluene.
Ketone-catalyzed photochemical C(sp3)–H chlorination
Han, Lei,Xia, Ji-Bao,You, Lin,Chen, Chuo
, p. 3696 - 3701 (2017/06/13)
Photoexcited arylketones catalyze the direct chlorination of C(sp3)–H groups by N- chlorosuccinimide. Acetophenone is the most effective catalyst for functionalization of unactivated C–H groups while benzophenone provides better yields for benzylic C–H functionalization. Activation of both acetophenone and benzophenone can be achieved by irradiation with a household compact fluorescent lamp. This light-dependent reaction provides a better control of the reaction as compared to the traditional chlorination methods that proceed through a free radical chain propagation mechanism.
